US6761749B1 - Method for the production of blister copper in suspension reactor - Google Patents
Method for the production of blister copper in suspension reactor Download PDFInfo
- Publication number
- US6761749B1 US6761749B1 US10/169,524 US16952402A US6761749B1 US 6761749 B1 US6761749 B1 US 6761749B1 US 16952402 A US16952402 A US 16952402A US 6761749 B1 US6761749 B1 US 6761749B1
- Authority
- US
- United States
- Prior art keywords
- slag
- concentrate
- copper
- reactor
- matte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/0047—Smelting or converting flash smelting or converting
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- This invention relates to a method of producing blister copper pyrometallurgically in a suspension reactor directly from Its sulfidic concentrate.
- a copper sulfide concentrate is fed into a suspension reactor, into which cooled and finely ground copper matte is also fed in order to bind the heat released from the concentrate.
- a well-known method of the prior art is to produce raw copper or blister copper from a sulfidic concentrate in several stages, whereby the concentrate is smelted in a suspension reactor, such as a flash-smelting furnace, with air or oxygen-enriched air, which results in copper-rich matte (50-75% Cu) and slag.
- a suspension reactor such as a flash-smelting furnace
- air or oxygen-enriched air which results in copper-rich matte (50-75% Cu) and slag.
- Copper matte formed in a flash-smelting furnace is converted in for example a Peirce-Smith type converter or flash converter into blister copper and refined further in an anode furnace.
- the production of blister copper from sulfidic concentrate directly in one process step in a suspension reactor is economically viable within certain boundary conditions.
- the greatest problems involved in the direct production of blister include copper slagging to slag, the large amount of slag formed and the large amount of heat released on burning the concentrate.
- the large amount of slag requires a large smelting unit in surface area, which affects the investment costs of the process.
- the copper content of the concentrate is high enough, typically at least 37% Cu, as for example at the Olympic Dam smelter in Australia, where the copper content of the concentrate exceeds 50%, it is possible to produce blister directly in one stage, since the thermal value of the concentrate is usually lower the higher the copper content of the concentrate. In fact, at high copper content the proportion of iron sulfide minerals is low. When using the previously described concentrate, high enough oxygen enrichment can be used and, as a result the amounts of gas remain moderate.
- Concentrate with a lower copper content can also be suitable for direct blister production, if it has an advantageous composition.
- blister copper is produced from concentrate in one stage, since the iron content is low and the resulting amount of slag is not significantly high.
- the production of copper in one stage with normal concentrates causes slagging of all the iron and other gangues. This type of method is described in U.S. Pat. No. 4,030,915.
- the basic concept behind the present method is that instead of the conventional method, where the additional heat is bound to the nitrogen in the gas, in this method the heat is bound to cooled matte.
- the oxygen enrichment can be raised as the proportion of matte grow's both with poor and rich copper concentrates. If the proportion of cooled and finely ground matte in the feed is very great, the oxygen enrichment can be raised significantly even with poor concentrates and direct blister production made economically viable.
- Another benefit of the method in the present invention is that the relative amount of slag generated in the suspension reactor decreases as the proportion of matte increases in the feed, whereby copper losses into slag decrease and the amount of copper circulated via slag cleaning also decreases.
- Iron silicate slag or calcium ferrite slag can be used in a blister furnace depending on the composition of the concentrate. If both matte and blister production take place in the same smelter so that the slag processing can be handled jointly, it is advantageous that both reactors use the same type of slag. If slag concentration is part of the slag processing then it is advantageous that the slag is iron silicate slag.
- the matte fed into the blister furnace may be matte produced in any kind of known smelting furnace.
- a single suspension smelting unit may be designed directly as a blister smelter depending on the copper content and composition of the available concentrates and on the amount and composition of the available matte.
- the slags are treated further in single-stage or preferably two-stage slag cleaning.
- the two-stage cleaning method includes either two electric furnaces or an electric furnace and a slag concentrating plant. If the slags are treated in a slag concentrating plant, the slag concentrate can be fed back into the suspension reactor. Blister copper goes for normal refining in an anode furnace.
- FIG. 1 shows a principle diagram of one arrangement of the invention, where one suspension smelting unit and an electric furnace are used, and
- FIG. 2 shows another, where two suspension smelting units, a slag concentrating plant and an electric furnace are used.
- the copper sulfide concentrate is fed with a flux and copper matte into the suspension smelting unit, which in this case is a flash-smelting furnace (FSF).
- FSF flash-smelting furnace
- Blister copper formed in a flash smelting furnace is conveyed to an anode furnace and refined there in the usual way and cast into anodes.
- the slag from the flash smelting furnace is treated in an electric furnace, when the slag may be either calcium ferrite or iron silicate slag.
- the blister copper generated in the electric furnace is taken directly to the anode furnace and the small amount of slag generated in the anode furnace is taken to the electric furnace.
- FIG. 2 shows a diagram according to the second alternative of the present invention, where there are two smelting units, one a blister furnace and th other where the copper matte to be fed Into the blister furnace is produced.
- copper sulfide concentrate and silicate containing flux such as sand is fed according to the prior art into the reaction shaft of the primary smelting reactor of the process with oxygen or oxygen-enriched gas.
- the reactor is a flash smelting furnace, but it could be some other reactor for the formation of matte.
- the concentrate to be fed Into this furnace is advantageously a poor or normal copper concentrate, with a copper content of around 20-31% Cu. Copper matte forms on the bottom of the lower section of the flash smelting furnace, th lower furnace, and on top of that fayelite slag, which contains some amount of copper.
- Copper concentrate which is a sulfide concentrate, is taken to the blister producing suspension reactor (FSF), but its copper content is preferably higher (Cu content over 31%) than the concentrate fed into the smelting furnace which produces matte.
- the copper matte form d in the matte producing furnace is granulated, ground and fed with the copper concentrate, silicate containing flux and oxygen or oxygen-enriched air into the blister reactor, which is also advantageously a flash smelting furnace.
- Blister copper is produced in the blister furnace, ready to be fed into the anode furnace, where the raw copper is fed in molten state.
- the copper to be refined in the anode furnace is cast into copper anodes.
- the slag formed in the matte producing smelting furnace is cooled slowly and ground.
- the slag is concentrated by flotation in a slag concentrating plant and the slag concentrate that is generated is taken back to the same matte producing smelting furnace. Since the copper content in the generated concentrate is often fairly high, it may also be conveyed to the blister furnace.
- the waste from the slag concentrating is waste slag, wit a Cu content of around 0.30-0.5%, preferably 0.3-0.35%.
- Slag formed in the blister reactor is taken advantageously to the electric furnace (EF) in molten state, for instance along channels.
- EF electric furnace
- the slag is reduced with coke, and the blister copper produced in the furnace is transferred directly to the anode furnace.
- the slag generated in the anode furnace is also taken to the same electric furnace.
- the electric furnace slag is cooled slowly like the slag from the matte producing suspension smelting furnace and taken to the slag concentrator for treatment along with the slag from the matte producing smelting furnace.
- Blister copper was produced in a suspension smelting furnace as shown in FIG. 1 .
- the flash smelting furnace feed is 83.7 t/h, composed as follows: Concentrate 36.1 t/h, slag concentrate 2.2 t/h, flux 4.4 t/h, matte 35.4 t/h and flue dust 5.6 t/h.
- composition of the concentrate is:
- the SiO 2 content of the flux fed into the furnace is 90%.
- the analysis of the copper matte is as follows:
- the amount of oxygen fed into the furnace is 13 400 Nm 3 /h and the amount of air 4140 Nm 3 /m, degree of oxygen enrichment is 74.6%.
- 35.6 t/h blister copper is produced in the flash, smelting furnace and its copper content is 99.41%.
- the amount of fayelite slag is 29.2 t/h and its composition is as follows: Cu 20%, Fe 28.7%, S 0.1% and SiO 2 21%.
- the amount of gas exiting the furnace is 29 100 Nm 3 t/h, the temperature 1320° C. and its analysis are: SO 2 42.3% and O 2 2.1%.
- the gas is routed to a waste heat boiler, from where the flue dust obtained is recirculated back to the flash smelting furnace.
- Slag from the flash smelting furnace and from the anode furnace are treated together in the electric furnace, whereby the amount of slag from the FSF is 701 t/h, Cu content 20% and the amount of slag from the anode furnace is 4.5 t/h and Cu content 60%.
- the coke feed is 30 t/h.
- the amount of blister copper produced in the electric furnace is 121 t/h and Cu content 99.35%.
- the blister copper is taken to the anode furnace for refining with the blister copper from the flash smelting furnace.
- the amount of slag is 557 t/h and the Cu content 4%. Since its Cu content is so high, the slag is conveyed for further processing to the slag concentrating plant.
- the slag concentrate has a Cu content of 38.4% and the waste slag a Cu content of 0.38%.
- This example case describes the solution shown in FIG. 2 .
- the material amounts of the feed and the output are calculated per 1000 kg concentrate fed into the primary smelting furnace.
- the primary smelting furnace in this case is a flash smelting furnace.
- the amount of flux sand, fed into the furnace is 88 kg, slag concentrate 70 kg and circulated precipitates 22 kg.
- the total furnace feed is thus 1180 kg, as dust circulation is not taken into account here.
- 172 Nm 3 air and 157 Nm3 oxygen are fed into the reaction shaft of the furnace, so that the oxygen enrichment is 57%.
- the amount of matte generated in the smelting furnace is 464 kg and its composition is Cu 70%, Fe 7.0% and S 21.2% and temperature 1280° C.
- the amount of slag is 568 kg, and its composition: Cu 2.6%, Fe 42%, S 0.7% and SiO 2 27% and temperature 1320° C.
- the matte formed in the primary smelting furnace is granulated, ground and the ground matte is fed into the suspension sm liting furnace in order to bind the heat generated in the furnace.
- concentrate is fed into the furnace, with the following composition: Cu 38%, Fe 29% and S 26% and 214 kg in amount.
- the flux which is again sand, is fed 44 kg in amount.
- the total feed is 710 kg, when th loss forming in grinding is taken into account.
- 50 Nm 3 air and 111 Nm 3 oxygen is fed into the blister furnace, so the oxygen enrichment is 72%.
- the amount of raw copper formed in the suspension smelting furnace in this case a flash smelting furnace, is 362 kg and its Cu content 98.8% and S content 0.6, with a temperature of 1280° C.
- the amount of slag forming in the flash smelting furnace is 239 kg and its composition is Cu 20%, Fe 31.2%, S 0.1% and SiO 2 21% and temperature 1300° C.
- the slag from the blister furnace is routed to the electric furnace in the same way as the slag from the anode furnace, where the amount of the slag is only 3kg and Cu content 60%. 10kg of coke is added. 44 kg of blister forms in the electric furnace, with a 96% Cu content. The amount of slag in the electric furnace is 188 kg and its composition is as follows: Cu 4%, Fe 27.3%, S 4.8% and SiO 2 17.6% .
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/FI2000/000004 WO2001049890A1 (en) | 1998-12-30 | 2000-01-04 | Method for the production of blister copper in suspension reactor |
Publications (1)
Publication Number | Publication Date |
---|---|
US6761749B1 true US6761749B1 (en) | 2004-07-13 |
Family
ID=8555865
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/169,524 Expired - Lifetime US6761749B1 (en) | 2000-01-04 | 2000-01-04 | Method for the production of blister copper in suspension reactor |
Country Status (17)
Country | Link |
---|---|
US (1) | US6761749B1 (de) |
EP (1) | EP1257676B1 (de) |
JP (1) | JP4936624B2 (de) |
KR (1) | KR100658405B1 (de) |
CN (1) | CN1167819C (de) |
AT (1) | ATE260994T1 (de) |
AU (1) | AU777665B2 (de) |
BR (1) | BR0016890A (de) |
CA (1) | CA2395995C (de) |
DE (1) | DE60008804T2 (de) |
EA (1) | EA003759B1 (de) |
MX (1) | MXPA02006652A (de) |
PL (1) | PL194875B1 (de) |
PT (1) | PT1257676E (de) |
RS (1) | RS49863B (de) |
TR (1) | TR200201715T2 (de) |
WO (1) | WO2001049890A1 (de) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050199095A1 (en) * | 2002-06-11 | 2005-09-15 | Pekka Hanniala | Method for producing blister copper |
US20080152558A1 (en) * | 2005-02-14 | 2008-06-26 | Outotec Oyj | Method for the Treatment of Copper-Bearing Materials |
US20100050811A1 (en) * | 2008-09-04 | 2010-03-04 | Nakakado Kenta | Method of smelting copper |
US20100050813A1 (en) * | 2008-09-04 | 2010-03-04 | Nakakado Kenta | Method of smelting copper |
AU2008337430B2 (en) * | 2007-12-17 | 2013-03-28 | Metso Metals Oy | Method for refining copper concentrate |
WO2016197201A1 (en) * | 2015-06-12 | 2016-12-15 | Glencore Technology Pty Limited | Method for treating copper concentrates |
US9733016B2 (en) | 2005-06-08 | 2017-08-15 | Sms Group Gmbh | Process and arrangement for extracting a metal from slag a containing said metal |
US10435769B2 (en) * | 2016-07-22 | 2019-10-08 | Outotec (Finland) Oy | Method for refining sulfidic copper concentrate |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FI115536B (fi) * | 2001-09-21 | 2005-05-31 | Outokumpu Oy | Menetelmä raakakuparin tuottamiseksi |
FI115638B (fi) * | 2002-12-05 | 2005-06-15 | Outokumpu Oy | Menetelmä kuonan käsittelemiseksi |
PL1759024T3 (pl) * | 2004-04-07 | 2014-12-31 | Outotec Oyj | Sposób konwertowania miedzi |
DE102006052181A1 (de) | 2006-11-02 | 2008-05-08 | Sms Demag Ag | Verfahren zur kontinuierlichen oder diskontinuierlichen Gewinnung eines Metalls oder mehrerer Metalle aus einer das Metall oder eine Verbindung des Metalls enthaltenden Schlacke |
JP5357536B2 (ja) * | 2008-12-09 | 2013-12-04 | シアングアング カッパー カンパニー リミテッド | 高含硫粗銅の陽極精錬方法 |
CN102605191B (zh) | 2012-04-16 | 2013-12-25 | 阳谷祥光铜业有限公司 | 一种铜精矿直接生产粗铜的方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2506557A (en) | 1947-04-03 | 1950-05-02 | Bryk Petri Baldur | Method for smelting sulfide bearing raw materials |
US4030916A (en) | 1975-01-08 | 1977-06-21 | Andreas M. Liniger | Process for recovering lead from the active material of used batteries |
US4599108A (en) * | 1984-07-18 | 1986-07-08 | Outokumpu, Oy | Method for processing sulphide concentrates and sulphide ores into raw material |
US5565016A (en) | 1994-02-17 | 1996-10-15 | Outokumpu Engineering Contractors Oy | Method for suspension smelting |
US6042632A (en) * | 1996-01-17 | 2000-03-28 | Kennecott Holdings Company | Method of moderating temperature peaks in and/or increasing throughput of a continuous, top-blown copper converting furnace |
US6096110A (en) * | 1997-04-14 | 2000-08-01 | Outokumpu Oyj | Method for cleaning slag in an electric furnace |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FI52358C (fi) * | 1974-11-11 | 1977-08-10 | Outokumpu Oy | Tapa valmistaa raakakuparia jatkuvasti yhdessä vaiheessa epäpuhtaasta sulfidisesta kuparirikasteesta tai -malmista . |
CA1245460A (en) * | 1985-03-20 | 1988-11-29 | Carlos M. Diaz | Oxidizing process for sulfidic copper material |
CA1294131C (en) * | 1985-11-18 | 1992-01-14 | Grigori Semion Victorovich | Process for reduction smelting of materials containing base metals |
AUPM657794A0 (en) * | 1994-06-30 | 1994-07-21 | Commonwealth Scientific And Industrial Research Organisation | Copper converting |
US5658368A (en) * | 1995-03-08 | 1997-08-19 | Inco Limited | Reduced dusting bath method for metallurgical treatment of sulfide materials |
-
2000
- 2000-01-04 CA CA2395995A patent/CA2395995C/en not_active Expired - Lifetime
- 2000-01-04 EP EP00901156A patent/EP1257676B1/de not_active Expired - Lifetime
- 2000-01-04 WO PCT/FI2000/000004 patent/WO2001049890A1/en active IP Right Grant
- 2000-01-04 MX MXPA02006652A patent/MXPA02006652A/es active IP Right Grant
- 2000-01-04 RS YUP-517/02A patent/RS49863B/sr unknown
- 2000-01-04 AT AT00901156T patent/ATE260994T1/de not_active IP Right Cessation
- 2000-01-04 AU AU21125/00A patent/AU777665B2/en not_active Expired
- 2000-01-04 CN CNB008181802A patent/CN1167819C/zh not_active Expired - Lifetime
- 2000-01-04 PT PT00901156T patent/PT1257676E/pt unknown
- 2000-01-04 DE DE60008804T patent/DE60008804T2/de not_active Expired - Lifetime
- 2000-01-04 KR KR1020027008676A patent/KR100658405B1/ko active IP Right Grant
- 2000-01-04 JP JP2001550417A patent/JP4936624B2/ja not_active Expired - Lifetime
- 2000-01-04 BR BR0016890-4A patent/BR0016890A/pt not_active IP Right Cessation
- 2000-01-04 PL PL355869A patent/PL194875B1/pl unknown
- 2000-01-04 US US10/169,524 patent/US6761749B1/en not_active Expired - Lifetime
- 2000-01-04 TR TR2002/01715T patent/TR200201715T2/xx unknown
- 2000-01-04 EA EA200200747A patent/EA003759B1/ru not_active IP Right Cessation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US2506557A (en) | 1947-04-03 | 1950-05-02 | Bryk Petri Baldur | Method for smelting sulfide bearing raw materials |
US4030916A (en) | 1975-01-08 | 1977-06-21 | Andreas M. Liniger | Process for recovering lead from the active material of used batteries |
US4599108A (en) * | 1984-07-18 | 1986-07-08 | Outokumpu, Oy | Method for processing sulphide concentrates and sulphide ores into raw material |
US5565016A (en) | 1994-02-17 | 1996-10-15 | Outokumpu Engineering Contractors Oy | Method for suspension smelting |
US6042632A (en) * | 1996-01-17 | 2000-03-28 | Kennecott Holdings Company | Method of moderating temperature peaks in and/or increasing throughput of a continuous, top-blown copper converting furnace |
US6096110A (en) * | 1997-04-14 | 2000-08-01 | Outokumpu Oyj | Method for cleaning slag in an electric furnace |
Non-Patent Citations (1)
Title |
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Victorovich et al, "Direct Production of Copper" Journal of Metals Sep. 1987 G.S. pp 42-46, vol. 39. |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050199095A1 (en) * | 2002-06-11 | 2005-09-15 | Pekka Hanniala | Method for producing blister copper |
US20080152558A1 (en) * | 2005-02-14 | 2008-06-26 | Outotec Oyj | Method for the Treatment of Copper-Bearing Materials |
US7811534B2 (en) * | 2005-02-14 | 2010-10-12 | Outotec Oyj | Method for the treatment of copper-bearing materials |
US9733016B2 (en) | 2005-06-08 | 2017-08-15 | Sms Group Gmbh | Process and arrangement for extracting a metal from slag a containing said metal |
AU2008337430B2 (en) * | 2007-12-17 | 2013-03-28 | Metso Metals Oy | Method for refining copper concentrate |
US20100050813A1 (en) * | 2008-09-04 | 2010-03-04 | Nakakado Kenta | Method of smelting copper |
US7955409B2 (en) * | 2008-09-04 | 2011-06-07 | Pan Pacific Copper Co., Ltd. | Method of smelting copper |
US7918917B2 (en) * | 2008-09-04 | 2011-04-05 | Pan Pacific Copper Co., Ltd. | Method of smelting copper |
US20100050811A1 (en) * | 2008-09-04 | 2010-03-04 | Nakakado Kenta | Method of smelting copper |
WO2016197201A1 (en) * | 2015-06-12 | 2016-12-15 | Glencore Technology Pty Limited | Method for treating copper concentrates |
EA035051B1 (ru) * | 2015-06-12 | 2020-04-22 | Гленкор Текнолоджи Пти Лимитед | Способ обработки медных концентратов |
US10781505B2 (en) | 2015-06-12 | 2020-09-22 | Glencore Technology Pty Ltd | Method for treating copper concentrates |
US10435769B2 (en) * | 2016-07-22 | 2019-10-08 | Outotec (Finland) Oy | Method for refining sulfidic copper concentrate |
Also Published As
Publication number | Publication date |
---|---|
ATE260994T1 (de) | 2004-03-15 |
CN1167819C (zh) | 2004-09-22 |
JP4936624B2 (ja) | 2012-05-23 |
EP1257676B1 (de) | 2004-03-03 |
EA003759B1 (ru) | 2003-08-28 |
PL355869A1 (en) | 2004-05-31 |
DE60008804T2 (de) | 2004-08-05 |
PL194875B1 (pl) | 2007-07-31 |
KR20020065635A (ko) | 2002-08-13 |
EP1257676A1 (de) | 2002-11-20 |
JP2003519288A (ja) | 2003-06-17 |
CA2395995C (en) | 2010-05-25 |
CA2395995A1 (en) | 2001-07-12 |
RS49863B (sr) | 2008-08-07 |
CN1415023A (zh) | 2003-04-30 |
EA200200747A1 (ru) | 2002-12-26 |
MXPA02006652A (es) | 2002-09-30 |
KR100658405B1 (ko) | 2006-12-15 |
DE60008804D1 (de) | 2004-04-08 |
YU51702A (sh) | 2005-03-15 |
AU777665B2 (en) | 2004-10-28 |
WO2001049890A1 (en) | 2001-07-12 |
TR200201715T2 (tr) | 2002-10-21 |
AU2112500A (en) | 2001-07-16 |
BR0016890A (pt) | 2002-10-08 |
PT1257676E (pt) | 2004-06-30 |
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